This thesis presents applications of the layer-by-layer (LbL) assembly technique in fabrication of thin films with a primary focus on design and development of electrochromic devices. The optical properties of electrochromic materials change as they alter between redox states. The morphology and properties of LbL-assembled thin films can be modified by varying several processing factors such as dipping duration, ion type, ion concentration, pH, molecular weight, and ionic strength. In the present work, several factors of LbL assembly process were manipulated to tailor electrochromic thin films of desired attributes. An electrochromic device (ECD) with fast optical switching speed was designed and constructed based on poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS). This device exhibited optical switching speeds of 31 and 6 ms for coloration and decoloration respectively, on a 60 mm2 area. Poly(aniline 2-sulfonic acid) (PASA) is a relatively new ionic polymer, and its electrochromic properties have not been previously investigated in much detail. PASA thin film showed several redox states corresponding to color changes from dark blue to gray as it passed different redox states. One particularly interesting and promising design for ECDs is dual electrochrome. Dual electrochrome ECDs based on PANI and polyaniline (PASA) are investigated in this thesis. The PANI/PASA thin film showed superior spectroelectrochemical properties compare to other ECDs reported here or elsewhere. An electrode with single wall carbon nanotubes (SWCNTs) coating was tested as the substrate for an ECD based on poly[2-(3-thienyl) ethoxy-4-butylsulfonate] (PTEBS) to examine performance of the electrochromic polymer on a substrate other than an indium tin oxide (ITO) electrode. Compared to ITO, the SWCNT based device exhibited superior properties. / Master of Science

Superplasticity and superionic conductivity (SIC), both thermally activated processes, have been independently observed in certain materials with a high diffusion coefficient in high temperature ranges. Intuitively, this observation leads one to the idea that both types of behavior may be inter-related with one another. Therefore, it is the purpose of this research to investigate, specifically, the deformation characteristics of two SIC's, Bi₂O₃ and YSZ (yttria-stabilized zirconia), and to attempt a correlation of their behavior. Compressive deformation of these two materials was conducted over a wide range of temperatures and at various strain rates in an effort to characterize the temperature and/or strain-rate dependences of any observed superplasticity. Steady-state flow stress values were utilized to calculate the strain-rate sensitivity, m, of the materials, as well as the activation energies (Q_C) of superplasticity. Next, the obtained values of Q_C. were compared to SIC activation energies from the literature. Bi₂O₃ exhibited structural superplasticity within the range of test conditions utilized. However, published values of SIC activation energy were lower than experimentally derived Q_C by a factor of four. Therefore, one is not able to state whether or not there is any correlation between the two behaviors. Unfortunately, YSZ exhibited brittle behavior over the entire temperature and strain-rate ranges, so the same analysis could not be performed. Furthermore, SEM micrographs showed that YSZ samples, as processed, did not possess the proper microstructure required for superplasticity. Hence, no final conclusions on YSZ can be drawn from this study. / Master of Science

Over the last several years, there has been widespread interest in the structure property behavior of ion containing polymers. Of particular interest are those materials termed ionomers which contain ionic groups that are typically less than 15 mole percent. These ionic interactions provides an additional means of controlling polymer structure and properties. In the conventional ionomers, the ionic groups are placed randomly along the polymeric backbone resulting in a network structure that is rather poorly defined. An alternate approach is to prepare ionomers where the ionic groups are placed at well defined locations along the polymer backbone such as the telechelic ionomers, block ionomers, or the segmented ionomers where the ionene polymers serve as an example. The structure-property behavior of all these three types of ionomers have been investigated in this study. The telechelic ionomers were based on either a polyisoprene (PIP) or polybutadiene (PBD) backbone. The PIP ionomers have been neutralized with various cations and neutralized to different levels. The bulk properties were found to be highly dependent on the nature of the cation, its valency, and its ionic radius. A series of sulfonated and carboxylated ionomers of similar molecular weight have been studied in order to compare the performance of sulfonated ionomers to that of the carboxylated counterpart. As expected, the nature of ionic association in the sulfonated ionomer was found to be much stronger than in the carboxylate ionomer. The extent of neutralization as well as variations in the non-ionic segment molecular was studied in the PBD telechelic ionomers. For the first time, a bimodal type of SAXS peak was observed for 2000 M̅_n, PBD ionomer. In the segmented ionene polymers, the effect of the non-ionic segment (PTMO) molecular weight, the nature of the counterion (Cl vs. Br vs. I), and the architecture of the ionene segment were investigated. From SAXS analysis, a change in the morphology was indicated when the PTMO segment molecular weight exceeded 3400 M̅_n. It was estimated that the interfacial region was very sharp in all the materials investigated. One of the main limitations of the ionene polymers discussed herein is that the material undergoes irreversible degradation at elevated temperature. It has been shown that with the addition of an ionic plasticizer such as zinc stearate, the softening temperature of the ionene polymer is lowered which allows thermal processing without a major loss of properties. A detailed morphological investigation of methacrylate based block ionomers was conducted. The effect of ionic block length, the architecture of the segments, and variations in the polarity of the glassy segments were investigated. Though the diblock materials exhibited poor tensile properties, the morphological features of these materials were very interesting. Multiple scattering peaks were observed in the diblock materials using SAXS. Both highly ordered as well as disordered regions were observed from TEM measurements. The spacing observed from TEM measurements correlates quite well with that observed from SAXS. Surprisingly, long range ordering was absent in the triblock ionomer with similar ion content. Finally, the spacing between the ionic domains were found to be a strong function of the ionic block length. / Ph. D.

Polymer electrolytes are indispensable in numerous electrochemical systems. Existing polymer electrolytes rarely meet all technical demands by their applications (e.g., high ionic conductivity and good mechanical strength), and new types of polymer electrolytes continue to be developed. In this dissertation, the molecular structure and dynamics of three emerging types of polymer electrolytes featuring Coulombic liquids, i.e., polymerized ionic liquids (polyILs), nanoscale ionic materials (NIMs), and polymeric ion gels, were investigated using molecular dynamics (MD) simulations to help guide their rational design. First, the molecular structure and dynamics of a prototypical polyILs, i.e., poly(1-butyl-3-vinylimidazolium hexafluorophosphate), supported on neutral and charged quartz substrates were investigated. It was found that the structure of the interfacial polyILs is affected by the surface charge on the substrate and deviates greatly from that in bulk. The mobile anions at the polyIL-substrate interfaces diffuse mainly by intra-chain hopping, similar to that in bulk polyILs. However, the diffusion rate of the interfacial mobile anions is much slower than that in bulk due to the slower decay of their association with neighboring polymerized cations. Second, the structure and dynamics of polymeric canopies in the modeling NIMs where the canopy thickness is much smaller than their host nanoparticle were studied. Without added electrolyte ions, the polymeric canopies are strongly adsorbed on the solid substrate but maintain modest in-plane mobility. When electrolyte ion pairs are added, the added counter-ions exchange with the polymeric canopies adsorbed on the charged substrate. However, the number of the adsorbed electrolyte counter-ions exceeds the number of desorbed polymeric canopies, which leads to an overscreening of the substrate's charge. The desorbed polymers can rapidly exchange with the polymers grafted electrostatically on the substrate. Finally, the molecular structure and dynamics of an ion gel consisting of PBDT polyanions and room-temperature ionic liquids (RTIL) were studied. First, a semi-coarse-grained model was developed to investigate the packing and dynamics of the ions in this ion gel. Ions in the interstitial space between polyanions exhibit distinct ordering, which suggests the formation of a long-range electrostatic network in the ion gel. The dynamics of ions slow down compared to that in bulk due to the association of the counter-ions with the polyanions' sulfonate groups. Next, the RTIL-mediated interactions between charged nanorods were studied. It was discovered that effective rod-rod interaction energy oscillates with rod-rod spacing due to the interference between the space charge near each rod as the two rods approach each other. To separate two rods initially positioned at the principal free energy minimum, a significant energy barrier (~several kBT per nanometer of the nanorod) must be overcome, which helps explain the large mechanical modulus of the PBDT ion gel reported experimentally. / Ph. D. / Polymer electrolytes are an indispensable component in numerous electrochemical devices. However, despite decades of research and development, few existing polymer electrolytes can offer the electrochemical, transport, mechanical, and thermal properties demanded by practical devices and new polymer electrolytes are continuously being developed to address this issue. In this dissertation, the molecular structure and dynamics of three emerging novel polymer electrolytes, i.e., polymerized ionic liquids (polyILs), nanoscale ionic materials (NIMs), and polymeric ion gels, are investigated to understand how their transport and mechanical properties are affected by their molecular design. The study of polyILs focused on the interfacial behavior of a prototypical polyILs supported on neutral and charged quartz substrates. It was shown that the structure and diffusion mechanism of the interfacial polyILs are sensitive to the surface charges of the substrate and can deviate strongly from that in bulk polyILs. The study of NIMs focused on how the transport properties of the dynamically grafted polymers are affected by electrolyte ion pairs. It was discovered that the contaminated ions can affect the conformation the polymeric canopies and the exchange between the “free” and “grafted” polymers. The study of polymeric ion gels focused on the molecular and mesoscopic structure of the ionic liquids in the gel and the mechanisms of ion transport in these gels. It was discovered that the ions exhibit distinct structure at the intermolecular and the interrod scales, suggesting the formation of extensive electrostatic networks in the gel. The dynamics of ions captured in simulations is qualitatively consistent with experimental observations.

Ionic electroactive polymers have been developed as mechanical sensors or actuators, taking advantage of the electromechanical coupling of the materials. This research attempts to take advantage of the chemomechanical and chemoelectrical coupling by characterizing the transient response as the polymer undergoes an ion exchange, thus using the polymer for ionic sensing. Nafion™ is a biocompatible material, and an implantable polymeric ion sensor which has applications in the biomedical field for bone healing research. An ion sensor and a strain gauge could determine the effects of motion allowed at the fracture site, thus improving rehabilitation procedures for bone fractures. The charge sensitivity of the material and the capacitance of the material were analyzed to determine the transient response. Both measures indicate a change when immersed in ionic salt solutions. It is demonstrated that measuring the capacitance is the best indicator of an ion exchange. Relative to a flat response in deionized water (±2%), the capacitance of the polymer exhibits an exponential decay of ~25% of its peak when placed in a salt solution. A linear correlation between the time constant of the decay and the ionic size of the exchanging ion was developed that could reasonably predict a diffusing ion. Tests using an energy dispersive spectrometer (EDS) indicate that 90% of the exchange occurs in the first 20 minutes, shown by both capacitance decay and an atomic level scan. The diffusion rate time constant was found to within 0.3% of the capacitance time constant, confirming the ability of capacitance to measure ion exchange. / Master of Science

The purpose of this thesis is the development and analysis of applications for ionic polymers as energy harvesting devices. The specific need is a self-contained energy harvester to supply renewable power harvested from ambient vibrations to a wireless sensor. Ionic polymers were investigated as mechanical to electrical energy transducers. An ionic polymer device was designed to harvest energy from vibrations and supply power for a wireless structural health monitoring sensor.The ionic polymer energy harvester is tested to ascertain whether the idea is feasible. Transfer functions are constructed for both the open-circuit voltage and the closed-circuit current. The impedance of the device is also quantified. Using the voltage transfer function and the current transfer function it is possible to calculate the power being produced by the device.Power generation is not the only energy harvesting application of ionic polymers, energy storage is another possibility. The ionic polymer device is tested to characterize its charge and discharge capabilities. It is charged with both DC and AC currents. An energy storage comparison is performed between the ionic polymers and capacitors. While the polymers performed well, the electrolytic capacitors are able to store more energy. However, the ionic polymers show potential as capacitors and have the possibility of improved performance as energy storage devices. Current is measured across resistive loads and the supplied power is calculated. Although the power is small, the ionic polymers are able to discharge energy across a load proving that they are capable of supplying power. / Master of Science

A transducer consisting of multiple layers of ionic polymer material is developed for applications in sensing, actuation, and control. The transducer consists of two to four individual layers each approximately 200 microns thick. The transducers are connected in parallel to minimize the electric field requirements for actuation. The tradeoff in deflection and force can be controlled by controlling the mechanical constraint at the interface. Packaging the transducer in an outer coating produces a hard constraint between layers and reduces the deflection with a force that increases linearly with the number of layers. This configuration also increases the bandwidth of the transducer. Removing the outer packaging produces an actuator that maintains the deflection of a single layer but has an increased force output. This is obtained by allowing the layers to slide relative to one another during bending. A Finite Element Analysis (FEA) method capable of modeling the structure of the multilayer transducers is developped. It is used to model the interfacial friction in multilayer transducers. Experiments on transducers with one to three layers are performed and the results are compared to Newbury's equivalent circuit model, which was modified to accommodate the multilayer polymers. The modification was performed on four different boundary conditions, two electrical the series and the parallel connection, and two mechanical the zero interfacial friction and the zero slip on the interface. Results demonstrate that the largest obstacle to obtaining good performance is water transport between the individual layers. Water crossover produces a near short circuit electrical condition and produces feedthrough between actuation layers and sensing layers. Electrical feedthrough due to water crossover eliminates the ability to produce a transducer that has combined sensing and actuation properties. Eliminating water crossover through good insulation enables the development of a small (5 mm x 30 mm) transducer that has sensing and actuation bandwidth on the order of 100 Hz. Due to the mechanical similarities of ionic transducers to biological muscles and their large flapping displacement capabilities we are studying the possibility of their use in flapping Micro Air Vehicle (MAV) application, as engines, controllers and sensors. The FEA modeling technique capable is used to design two ionic polymers actuated flapping wings. / Master of Science

No / Phosphonium tosylates have been investigated as solvents for the Diels¿Alder reactions of isoprene with methyl acrylate, but-3-en-2-one and acrylonitrile. The reactions with oxygen-containing dienophiles showed high regioselectivity. Graphic

No / Traditionally materials with the fluorite and perovskite structures have dominated the research in the area of oxide ion/proton conducting solid electrolytes. In such cases, the key defects are oxide ion vacancies, and conduction proceeds via a simple vacancy hopping mechanism. In recent years, there has been growing interest in alternative structure types, many of which contain tetrahedral moieties. For these new systems, an understanding of the accommodation of defects and the nature of the conduction mechanism is important for the optimisation of their conductivities, as well as to help target related structures that may display high oxide ion/proton conduction. Computer modelling studies on a range of systems containing tetrahedral moieties are presented, including apatite-type La9.33+xGe6O26+3x/2, cuspidine-type La4Ga2-xTixO9+x/2 and La1-xBa1+xGaO4-x/2. The type of anion defect (vacancy or interstitial), their location and the factors affecting their incorporation are discussed. In addition, modelling data to help to understand their conduction mechanisms are presented, showing novel aspects including the important role of the tetrahedral moieties in the conduction processes.

No / Traditionally materials with the fluorite and perovskite structures have dominated the research in the area of oxide ion/proton conducting solid electrolytes. In such cases, the key defects are oxide ion vacancies, and conduction proceeds via a simple vacancy hopping mechanism. In recent years, there has been growing interest in alternative structure types, many of which contain tetrahedral moieties. For these new systems, an understanding of the accommodation of defects and the nature of the conduction mechanism is important for the optimisation of their conductivities, as well as to help target related structures that may display high oxide ion/proton conduction. Computer modelling studies on a range of systems containing tetrahedral moieties are presented, including apatite-type La9.33+xGe6O26+3x/2, cuspidine-type La4Ga2¿xTixO9+x/2 and La1¿xBa1+xGaO4¿x/2. The type of anion defect (vacancy or interstitial), their location and the factors affecting their incorporation are discussed. In addition, modelling data to help to understand their conduction mechanisms are presented, showing novel aspects including the important role of the tetrahedral moieties in the conduction processes